CN108884307A

CN108884307A - Use the article of manufacture of the improved melt polycarbonate of impact property

Info

Publication number: CN108884307A
Application number: CN201780019898.9A
Authority: CN
Inventors: D·德尔阿瓜埃尔南德斯; M·D·马丁内兹卡诺瓦斯; R·D·范德盖姆伯尔
Original assignee: SABIC Global Technologies BV
Current assignee: SABIC Global Technologies BV
Priority date: 2016-02-26
Filing date: 2017-02-22
Publication date: 2018-11-23
Anticipated expiration: 2037-02-22
Also published as: CN108884307B; CN108779323A; US20190048183A1; WO2017145076A1; CN108779323B; EP3420031A1; KR20180109081A; US20190055400A1; WO2017145075A1; EP3420030A1

Abstract

This disclosure relates to the product formed by the composition comprising melt polycarbonate component and interfacial polycarbonate component.Resulting product shows improved mechanical performance than the product of the polycarbonate formation prepared according to conventional melt polymerization.

Description

Use the article of manufacture of the improved melt polycarbonate of impact property

Invention field

This disclosure relates to the method for producing polycarbonate according to melt polymerization process.

Background of invention

Polycarbonate (PC) is used for various applications in many industry due to its multi-functional and ideal property.Poly- carbon Acid esters provides the high grade of transparency, and has high impact properties and high-fire resistance.Polycarbonate is generally according to two kinds of commodity production sides The production of one of method (two-phase interface method and melt transesterification method).Interfacial process include as acid acceptor alkaline reagent and In the presence of the amine of catalyst, make at least one dihydroxy compounds (usually dihydroxy aromatic compounds) and phosgene molten It is reacted in agent.Melt transesterification method is well known in the art, and is used in the presence of ester exchange catalyst may be selected, Polycarbonate is prepared by diaryl carbonate and dihydroxy compounds reaction.Other methods to come in handy be often this two Directly variation or the simple combination of kind main method.

Polycarbonate is transparent engineering thermoplasties, with other transparent polymers such as polymethyl methacrylate or poly- Terephthalic acids butanediol ester, which is compared, has improved impact property.However, at low temperature, brittleness may be presented in polycarbonate resin Behavior, and the impact property of material may be insufficient for certain application requirements.

In order to avoid these problems, the additive of several types can be blended with polycarbonate resin.Use additive If elastomer (ABS or MBS) or reinforcing fiber are a kind of well-known strategies.This enhancing additive is usually in preparation steps In with polycarbonate blending, unfortunately, polycarbonate becomes opaque.

U.S. Patent number 5,504,177 and 6,066,700, which is intended to describe to produce using siloxanes at low temperature, to be had well The transparent material of impact property.Due to reactive lower (such as in diphenyl carbonate DPC) that carbonate group uses, Described in copolymerization strategy increase additional cost and complexity.

U.S. Patent number 5,959,065 is intended to describe in polycarbonate chain using " high volume " end-capping reagent to improve poly- carbon The impact property of acid esters material generates any negative effect without the transparency to material.However, the strategy is new due to adding Monomer and the cost for increasing resin, and under the specific condition for obtaining polycarbonate by melting method, it is difficult to change work Skill adds the additional monomers.

The disclosure solves these and other disadvantages of the prior art.

Summary of the invention

In the disclosure, it is shown that be about 20cm for melt volume rate (MVR)³/min(1.2Kg-300℃ISO 1133) to about 30cm³The low viscosity grade of/min, the improvement of the impact property of polycarbonate (PC) molten resin.By that will melt Melting PC resin and other interface PC resin alloys realizes this improvement.Compared with traditional end-capping group of melting PC resin, boundary Face PC resin component has different types of sealing end.Compared with typical case's end group (BPA) present in the molten resin, interface PC resin End-capping group be based on using bulky molecule (phenol, phosgene, to cumylphenol, p-tert-butylphenol).

By the way that a kind of PC of interface grade of the different proportion blocked based on 100% pair of cumylphenol is added to melting PC tree The ends concentration for increasing large volume in rouge improves melt material compared with the same resin without interfacial polycarbonate Impact property.For example, this addition can increase the bulkiness of end group without increase-OH (for example, reactivity).

Although all aspects of this disclosure can description and requirement in specific legal rank (such as the legal rank of system) Protection, but this is merely for convenience, and it will be understood by those skilled in the art that each aspect of the disclosure can be any legal It is described and claimed as in rank.Unless expressly stated otherwise, it is otherwise never intended to any method as described herein or aspect It is construed to require to execute its step with particular order.Therefore, in claims or description, claim to a method is without specific old When stating the step and being limited to particular order, it is not intended to infer the sequence in any way.This is suitable for any possible non-table The basis for interpretation reached is exported including the logical problem about step or the arrangement of operating process from grammatical organization or punctuation mark Ordinary meaning or specification described in aspect quantity or type.

It will partly illustrate in terms of other of the disclosure and partly will be apparent from the description in the following description, or Person can be understood by the practice of the disclosure.By the element and combination particularly pointed out in appended claims, will realize and The advantages of obtaining the disclosure.It should be appreciated that foregoing general description and following detailed description are all exemplary and explanation Property, it is not the limitation to the claimed disclosure.

Brief description

Fig. 1 shows the impact property figure of the blend of interface at different temperatures and melt polycarbonate.

Fig. 2 shows the impact property of the blend with different amounts of interface and melt polycarbonate with the change of temperature Change.

Fig. 3 shows impact property with the percentage composition of large volume end-capping group in interface and melt polycarbonate blend Variation.

Fig. 4 shows the variation in 10 DEG C of impact properties with the content of interfacial polycarbonate present in blend.

Fig. 5 shows the variation in 5 DEG C of impact properties with the content of interfacial polycarbonate present in blend.

Fig. 6 shows the variation in 0 DEG C of impact property with the content of interfacial polycarbonate present in blend.

Fig. 7 shows the variation in -1 DEG C of impact property with the content of interfacial polycarbonate present in blend.

Detailed description of the invention

Although the impact property that " high volume " end-capping reagent can be used for improving polycarbonate is negative without generating to transparency It influences, but these high volume end-capping reagents are used primarily in interfacial polymerization process.Although silicone additives can be used for interfacial polymerization Journey is to provide clear polycarbonate at low temperature with good impact property, but siloxanes can increase unnecessary cost simultaneously And it is not easily applicable to melt polycarbonate polymerization process (reactivity of carbonate source diphenyl carbonate is lower).Therefore, have with The melt polycarbonate resin of the suitable performance of interfacial polycarbonate resin be it is desirable that.

In general, in the presence of ester exchange catalyst, polycarbonate can be by molten condition in melt polymerization process Under prepare dihydroxy compounds (one or more) and carbonate source coreaction, the carbonate source such as diphenyl carbonate, Or in one aspect more specifically, carbonic ester such as two (methyl salicyl) carbonic ester of activation.In melt polymerization process, reaction Mixture may include melt transesterification catalyst, dihydroxy compounds, carbonate source and phenol by-product.More specifically, molten In the presence of melting ester exchange catalyst, polycarbonate can pass through the melting state transesterification reaction of dihydroxy compounds and diphenyl carbonate To prepare.With the progress of reaction, diphenyl carbonate can be consumed, while generate phenol by-product.

In one aspect, melt polymerization mixture may include melt transesterification catalyst.Melt transesterification catalyst It is well known in the art, however it is not limited to examples disclosed herein.Illustrative melt transesterification catalyst is disclosed in In U.S. Patent number 7,365,149,7,547,799,7,619,053 and 7,671,165.

In some respects, melt transesterification catalyst may include at least one α and/or β ester exchange catalyst.α catalyst Or first catalyst usually can be lower than β or the more thermostabilization of the second catalyst and volatility.Therefore, if in high temperature below It is used in polymerization stage, α catalyst may be more useful to melt polymerization.In all fields, α catalyst may include metal or Ion (cation or anion).In further example, α catalyst may include metal cation and anion.At one In specific example, cation can be the alkali or alkaline earth metal comprising Li, Na, K, Cs, Rb, Mg, Ca, Ba, Sr, or at least A kind of combination comprising aforementioned substances.Anion can be hydroxyl (OH^-), superoxides (O^2-), mercaptides (HS^-), vulcanization Object (S^2-)、C_1-20Alkoxide, C_6-20Fragrant oxide, C_1-20Carboxylate radical, phosphate radical (including hydrogen phosphate), C_1-20Phosphonate radical, sulfate radical (including bisulfate ion), inferior sulfate radical (including bisulfite and inclined bisulfite), C_1-20Sulfonate radical, carbonate (including Bicarbonate radical), or the combination comprising at least one aforementioned substances.On the other hand, it is possible to use include alkaline-earth metal ions and alkali The acylate of metal ion.The acylate that can be used as catalyst passes through formic acid, acetic acid, stearic acid and ethylenediamine tetra-acetic acid (EDTA) alkali and alkaline earth metal ions salt explanation.Catalyst may also include the salt of non-volatile inorganic acid." non-volatile " is Refer to the compound referred at ambient temperature and pressure without apparent vapour pressure.Particularly, these compounds are usually carrying out It is non-volatile at a temperature of polycarbonate melt polymerization.The salt of non-volatile acid is the alkaline earth of the alkali metal salt of phosphorous acid, phosphorous acid The alkali salt of metal salt, the alkali metal salt of phosphoric acid and phosphoric acid.

Exemplary α ester exchange catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, Calcium hydroxide, barium hydroxide, lithium formate, sodium formate, potassium formate, cesium formate, lithium acetate, sodium acetate, potassium acetate, lithium carbonate, carbon Sour sodium, potassium carbonate, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, phenol lithium, sodium phenate, potassium phenate, sulphur Sour sodium, potassium sulfate, NaH₂PO₃、NaH₂PO₄、Na₂H₂PO₃、KH₂PO₄、CsH₂PO₄、Cs₂H₂PO₄、Na₂SO₃、Na₂S₂O₅, methanesulfonic acid Sodium, methanesulfonic acid potassium, toluenesulfonic acid sodium salt, potassium toluene sulfonate, ethylenediamine tetra-acetic acid magnesium disodium (EDTA magnesium disodium salt), or comprising at least A kind of combination of aforementioned substances.It should be understood that previous list is exemplary, this should not be considered limited to.

In one aspect, α ester exchange catalyst is the α catalyst comprising alkali or alkaline earth metal salt.In an example Property aspect, ester exchange catalyst may include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, NaH₂PO₄, or the combination comprising at least one aforementioned substances.

According to the condition of melt polymerization, the amount of α catalyst can be widely varied, and can be about 0.001 micromole (μ Mol) to about 500 μm of ol.In other respects, the amount of beta catalyst used can be based on dihydroxy used in melt polymerization The total mole number of compound.

On the other hand, beta catalyst, i.e. the second ester exchange catalyst, can be optionally included in melt polymerization process, Condition is the required performance including will not significantly, adversely influence polycarbonate of this second ester exchange catalyst.Beta catalyst It may include quaternary ammonium compound, seasonCompound includes aforementioned at least one combination.Illustrative ester exchange catalyst can be with It further comprise above-mentioned formula (R³)₄Q⁺The combination of the phase transfer catalyst of X, wherein each R³It is identical or different, and be C_1-10Alkane Base；Q is nitrogen or phosphorus atoms；X is halogen atom or C_1-8Alkoxy or C_6-18Aryloxy group.Illustrative phase transfer catalyst salt includes, For example, [CH₃(CH₂)₃]₄NX、[CH₃(CH₂)₃]₄PX、[CH₃(CH₂)₅]₄NX、[CH₃(CH₂)₆]₄NX、[CH₃(CH₂)₄]₄NX、CH₃ [CH₃(CH₂)₃]₃NX and CH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl^-、Br^-、C_1-8Alkoxy or C_6-18Aryloxy group.

The example of this β ester exchange catalyst includes：Tetrabutylammonium, hydroxide methyltributylammoni,m, acetic acid four Butyl ammonium, tetrabutylphosphoniuhydroxide hydroxideTetrabutylphosphoniuacetate acetateThe phenol tetrabutylOr the group comprising at least one aforementioned substances It closes.Other melt transesterification catalysts include alkali salt or alkali metal salt.In the various aspects for needing beta catalyst, β catalysis Agent can be less than or equal to 10, particularly smaller or equal than 5 relative to the molar ratio of α catalyst, more specifically less than or equal to 1, more specifically less than or equal to 0.5.In other respects, melt polymerization disclosed herein is used only α as described above and urges Agent, and substantially free of any beta catalyst.As defined herein, substantially free can refer to beta catalyst from melting It is excluded in polymerization reaction.In one aspect, the total weight based on all components used in melt polymerization, beta catalyst Amount is less than about 10ppm, especially less than 1ppm, more specifically less than about 0.1ppm, more specifically less than or is equal to about 0.01ppm, more specifically less than or equal to about 0.001ppm.

In all fields, melt polymerization process disclosed herein may include dihydroxy compounds.The dihydroxy of the disclosure Formula HO-R can be had by closing object¹- OH comprising the dihydroxy compounds of formula (1)：

HO-A¹-Y¹-A²-OH (1)

Wherein Y¹、A¹And A²As described above.It further include the bisphenol compound of general formula (2)：

Wherein R^aAnd R^bHalogen atom or monovalent hydrocarbon respectively are represented, and can be identical or different；P and q are each independently The integer of 0-4；And X^aOne of the group of representative formula (3)：

Wherein R^cAnd R^dIt is independently represented each other hydrogen atom or monovalent linear or cyclic hydrocarbon group, R^eIt is bivalent hydrocarbon radical.

In all fields, the example of suitable dihydroxy compounds is included in U.S. Patent number 4,217,438 with title Or the hydrocarbon that dihydroxy disclosed in chemical formula (general formula or specific formula) replaces.The non-row of the specific example of suitable dihydroxy compounds His list includes following：Resorcinol, 4- bromine resorcinol, quinhydrones, 4,4 '-dihydroxybiphenyls, 1,6- dihydroxy naphthlene, 2,6- bis- Hydroxyl naphthalene, two (4- hydroxy phenyl) methane, two (4- hydroxy phenyl) diphenyl methanes, two (4- hydroxy phenyl) -1- naphthyl methanes, 1,2- bis- (4- hydroxy phenyl) ethane, 1,1- bis- (4- hydroxy phenyl) -1- diphenylphosphino ethane, 2- (4- hydroxy phenyl) -2- (3- hydroxyl Phenyl) propane, two (4- hydroxy phenyl) phenylmethanes, 2,2- bis- (4- hydroxyl -3- bromophenyl) propane, 1,1- bis- (hydroxy phenyl) Pentamethylene, 1,1- bis- (4- hydroxy phenyl) hexamethylene, 1,1- bis- (4- hydroxy phenyl) isobutene, 1,1- bis- (4- hydroxy phenyl) ring Dodecane, trans- -2,3- bis- (4- hydroxy phenyl) -2- butylene, 2,2- bis- (4- hydroxy phenyl) adamantane, α, (the 4- hydroxyl of α '-two Phenyl) toluene, two (4- hydroxy phenyl) acetonitriles, 2,2- bis- (3- methyl -4- hydroxy phenyl) propane, (3- ethyl -4- hydroxyl of 2,2- bis- Base phenyl) propane, 2,2- bis- (3- n-propyl -4- hydroxy phenyl) propane, 2,2- bis- (3- isopropyl -4- hydroxy phenyl) propane, 2,2- bis- (3- sec-butyl -4- hydroxy phenyl) propane, 2,2- bis- (3- tert-butyl-hydroxy phenyl) propane, (the 3- hexamethylene of 2,2- bis- Base -4- hydroxy phenyl) propane, 2,2- bis- (3- allyl -4- hydroxy phenyl) propane, (3- methoxyl group -4- hydroxy benzenes of 2,2- bis- Base) propane, 2,2- bis- (4- hydroxy phenyl) hexafluoropropane, chloro- 2,2- bis- (4- hydroxy phenyl) ethylene of 1,1- bis-, 1,1- bis- be bromo- 2,2- bis- (4- hydroxy phenyl) ethylene, 1,1- bis- chloro- 2,2- bis- (5- phenoxy group -4- hydroxy phenyl) ethylene, 4,4 '-dihydroxy two Benzophenone, 3,3- bis- (4- hydroxy phenyl) -2- butanone, 1,6- bis- (4- hydroxy phenyl) -1,6- acetyl butyryl, (the 4- hydroxyl of ethylene glycol two Base phenyl) ether, two (4- hydroxy phenyl) ethers, two (4- hydroxy phenyl) thioethers, two (4- hydroxy phenyl) sulfoxides, two (4- hydroxy benzenes Base) sulfone, 9,9- bis- (4- hydroxy phenyl) fluorine, 2,7- dihydroxy pyrene, 6,6 '-dihydroxy -3,3,3 ', 3 '-tetramethyl spiral shells (two) two Hydrogenate indenes (" spirobindene expires diphenol "), 3,3- bis- (4- hydroxy phenyl) phthalide, 2,6- dihydroxy dibenzo Dui bioxin, 2,6- bis- Hydroxyl thianthrene, 2,7- dihydroxy Fen Evil thiazine (phenoxathin), 2,7- dihydroxy -9,10- dimethylphenazine, 3,6- dihydroxy Base dibenzofurans, 3,6- dihydroxy dibenzothiophenes, 2,7- dihydroxy carbazole, 3,3- bis- (4- hydroxy phenyl) benzo [c] pyrrole Ketone, 2- phenyl -3,3- bis--(4- hydroxy phenyl) benzo [c] pyrrolones (PPPBP) etc. are coughed up, and includes at least one kind aforementioned two The mixture of hydroxy compounds.

It on the other hand, can include 1,1- bis- (4- hydroxy phenyl) by the example for the bisphenol compound type that formula (3) indicate Methane, 1,1- bis- (4- hydroxy phenyl) ethane, 2,2- bis- (4- hydroxy phenyl) propane (referred to hereinafter as " bisphenol-A " or " BPA "), 2,2- Two (4- hydroxy phenyl) butane, 2,2- bis- (4- hydroxy phenyl) octane, 1,1- bis- (4- hydroxy phenyl) propane, (the 4- hydroxyl of 1,1- bis- Base phenyl) normal butane, 2,2- bis- (4- hydroxyl -1- aminomethyl phenyl) propane and 1,1- bis- (4- hydroxyl -2-methyl-2-phenylpropane base) propane.It can also To use the combination including at least one aforementioned dihydroxy compounds.In other various aspects, can be used containing substituted or not The bis-phenol of substituted hexamethylene unit, such as the bis-phenol of formula (4)：

Wherein each R^fIt independently is hydrogen, C_1-12Alkyl or halogen；And each R^gIt independently is hydrogen or C_1-12Alkyl.It takes Dai Ji can be aliphatic or aromatics, straight chain, cricoid, bicyclic, branch, saturated or unsaturated.For example, this Bis-phenol containing hexamethylene is the reaction product of 2 moles of phenol Yu 1 molar isophorone, and can be used for preparing has high-vitrification The carbonate polymer of transition temperature and high heat distortion temperature.Polycarbonate containing cyclohexyl bisphenol, or include at least one The combination of kind aforementioned substances and other double phenol polycarbonates, by Bayer Co. with trade nameIt provides.

In other respects, in addition useful dihydroxy compounds is with formula HO-R¹Those of-OH compound comprising The aromatic dihydroxy compound of formula (4)：

Wherein each R^hIt is independently halogen atom, C_1-10Alkyl (such as C_1-10Alkyl), halogen replace C_1-10Alkyl (such as halogen The C that element replaces_1-10Alkyl), and n=0-4.Halogen is usually bromine.

On the other hand, branching agent include containing at least three kinds selected from hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl and its Mix the polyfunctional group organic compound of functional group.Specific example includes trimellitic acid, trimellitic anhydride, trimellitic acid tri-chlorination Object, three p-hydroxybenzene ethane, isatin-bis-phenol, triphenol TC (1,3,5- tri- ((p-hydroxybenzene) isopropyl) benzene), triphenol PA (4 (4 (1,1- bis- (p-hydroxybenzene)-ethyl) alpha, alpha-dimethylbenzyl) phenol), 4- chloroformyl phthalic anhydride, 1,3,5- Benzenetricarboxylic acid and benzophenone tetrabasic carboxylic acid.Branching agent can be added with the level of 0.05-2.0 weight %.Branching agent and preparation branching The method of polycarbonate describes in U.S. Patent number 3,635,895 and 4,001,184.Consider all types of polycarbonate ends Base can be used in thermoplastic compounds.

In one aspect, melt polymerization process disclosed herein may include carbonate source.For example, diaryl carbonate is available Make the carbonate source in melt polymerization process.Exemplary diaryl carbonate used according to the invention is disclosed in U.S. Patent number 7,365,149, in 7547,799,7,619,053 and 7,671,165.It, can in these patents in disclosed diaryl carbonate The non-ester substituted diaryl carbonate used may include, for example, diphenyl carbonate, carboxylol ester, two (chlorobenzene of carbonic acid Base) ester, m-cresyl and carbonic acid dinaphthyl ester.Some specific and non-limiting examples of disactivation carbonic ester are two (o- first Base phenyl) carbonic ester, two (to cumyl phenyl) carbonic esters, two (p- (1,1,3,3- tetramethyl) butyl phenyl) carbonic esters and two (adjacent cyano-phenyl) carbonic ester.The asymmetrical array of these structures also is used as disactivation carbonic ester.

The carbonic ester of activation can be used in melt polymerization process.As used herein, term " carbonic ester of activation " is defined as The diaryl carbonate more more reactive than diphenyl carbonate in ester exchange reaction.Diaryl carbonates activation or that ester replaces Ester can increase ester exchange reaction rate so that melt polymerization in a small amount of equipment, at reduced temperatures and/or most Occur in the short residence time.The specific non-limiting example of activated carbon acid esters includes：Two (O-methoxy carbonyl phenyl) carbonic acid Ester, two (Chloro-O-Phenyl) carbonic esters, two (O-Nitrophenylfluorone) carbonic esters, two (adjacent acetylphenyl) carbonic esters, two (adjacent phenyl ketones Phenyl) carbonic ester, two (adjacent Fonnylphenyl) carbonic esters.The example for the diaryl carbonate that specific ester replaces includes but unlimited In two (methyl salicyl) carbonic esters (CAS registration number 82091-12-1) (also referred to as BMSC or two (O-methoxy carbonyl phenyls) Carbonic ester), two (ethyl salicyl) carbonic esters, two (propyl salicyl) carbonic esters, two (butyl salicyl) carbonic esters, two (benzyls Base salicyl) carbonic ester, two (methyl -4- chlorine water Yankee) carbonic esters etc..In one aspect, due to lower molecular weight and Higher vapour pressure, two (methyl salicyl) carbonic esters are used as the activated carbonate in melt polycarbonate synthesis.Work as presence It is alkyl, naphthenic base or cyanogen that expection, which will not generate some non-limiting examples of the disactivation group of activated carbonate, when ortho position Base.

According to the aspect of present disclosure, melt polycarbonate resin can derive from diaryl carbonate source.As tool Body example, melt polycarbonate resin can derive from diphenyl carbonate.

In one aspect, end-capping reagent (also referred to as chain terminating agent) can be optionally used for restriction molecule amount growth rate, and because Molecular weight in this control polycarbonate.Illustrative chain terminating agent includes that certain single phenolic compounds (have individually free hydroxyl The phenyl compound of base), mono-carboxylic acid chlorides and/or monochlorinated formic acid esters.The example of phenolic chain stoppers has phenol and C₁-C₂₂ Alkyl-substituted phenol, as p -cumylphenol, resorcinol monobenzoate and p-butylphenol and tert-butyl phenol, cresols and The monoether (such as p methoxy phenol) of diphenol.Can specifically refer to branched alkyl chain substituents containing 8 to 9 carbon atoms Alkyl-substituted phenol.Certain single phenol ultraviolet absorbing agents also are used as end-capping reagent, for example, the 2- dihydroxy benaophenonel that replaces of 4- and Monoesters such as resorcinol monobenzoate, 2- (2- hydroxyaryl)-benzotriazole of its derivative, salicylic acid aryl ester, diphenol And its derivative, 2- (2- hydroxyaryl) -1,3,5-triazines and its derivative etc..

On the other hand, end group can derive from carbonyl source (i.e. diphenyl carbonate), be selected from monomer ratio, not exclusively gather The end-capping group of conjunction, chain rupture etc. and any addition, and may include can derived from functional group, such as hydroxyl, carboxylic acid group etc.. In one aspect, the end group of polycarbonate, including polycarbonate resin as herein defined may include from two virtue of carbonic acid The structural unit of base ester, such as dipheryl carbonate base ester, wherein structural unit can be end group.On the other hand, end group is from work The carbonic ester of change.These end groups can be from the Arrcostab and carbonate polymer last-in-chain(LIC) of the activated carbonate suitably replaced The ester exchange reaction of the hydroxyl at end, condition are wherein hydroxyl and the ester carbonyl group from activated carbonate rather than and activated carbonate Carbonic acid carbonyl reaction.In this way, from containing ester compounds or deriving from activated carbonate and be present in melt polymerization The structural unit of substructure in reaction can form ester terminal.

In various aspects of the disclosure, melt polymerization polycarbonate compositions can have less than about 1500ppm, be less than about 1000ppm or fries (Fries) content less than about 800ppm.It herein include the endpoint lower than 1500ppm.With the poly- carbon in interface Acid esters polymerizate is compared, according to polycarbonate prepared by melt polymerization process or activated carbonate melting method, as the U.S. is special It is presented in benefit number 5,151,491 and 5,142,018, usually contains the fries product of significant concentration.Although poly- in fusion method Low-level fries product can be allowed in carbonic ester product, but the presence of the fries product of higher amount may be to poly- The performance characteristic of carbonic ester such as mouldability and impact strength have a negative impact.By appropriate adjustment, may be melted poly- Conjunction process is to obtain the gained polycarbonate compositions with specific fries concentration.

Fries product or fries' rearrangement are produced as the side reaction occurred during melt polymerization polycarbonate Raw.Term " fries product " is defined as the structural unit of product polycarbonate, provides after product polycarbonate hydrolysis The dihydroxy aromatic compounds that carboxyl replaces, with one or two of the dihydroxy aromatic compounds replaced with the carboxyl The adjacent carboxyl of hydroxyl.Product " fries product " may be used as the site of polycarbonate chain branching, to influence poly- carbonic acid The mobility of ester and other properties.During preparing polycarbonate, fries' rearrangement, which indicates to exist in polycarbonate, to be had The repetitive unit of following formula (7)：

Wherein R^a、R^b, p, q and X^aAs defined above.R^cIt can be hydroxyl or carbonic ester or ether.Polymer chain can pass through Carbonic ester or ether are formed.R^dIt can be hydrogen or substituted aryl.Polymer chain can be formed by substituted aryl.For example, Following rearrangement (linear fries, branch/ether fries and sour fries) may occur：

Linear fries

Branch/ether fries

Sour fries

By changing temperature and/or reaction time, the total of branching fries' rearrangement can be adjusted in melt polymerization process Amount.Further, it is also possible to change melt polymerization reagent.For example, alkali metal hydroxide such as sodium hydroxide is used as using melting legal system The catalyst of standby polycarbonate.Although alkali metal hydroxide is to have for raw material is converted into the conversion ratio of product polycarbonate The catalyst of effect, but tend to produce the Fries rearrangement product of high relative contents.This may occur, because being formed at high temperature By-product include fries' rearrangement along the carbonate unit of the polymer chain of growth.

In various aspects of the disclosure, the fries weight of the carbonate unit of the polymer chain along growth can also be measured Row, to ensure that technique adjustment provides the desired amount of fries' rearrangement.The content of various fries components can pass through in polycarbonate Nuclear magnetic resonance (NMR) analysis determines.NMR corresponding to branch's fries structure, linear fries structure and sour fries structure Peak can be integrated to obtain total fries content.Can the integral based on the proton 1H NMR signal of fries component than eight The integral of polycarbonate proton obtains quantifying for fries' rearrangement content and polycarbonate aryl hydroxy end group content, such as implements It is specifically described in example.In other respects, fries content can be surveyed by high-efficient liquid phase chromatogram HPLC or other known methods Amount, such as potassium hydroxide (KOH) Methanol Decomposition of resin, and can be with parts per million (ppm) report.

In various aspects of the disclosure, melt polymerization process can carry out in series reaction device, wherein can control Operating condition such as temperature and pressure.In general, melt polymerization device system includes that oligomer forms part and polymer molecular weight Construct part.The device type used in these each parts is not particularly limited, it may include such as mixing arrangement, stirring or The container or reactor that do not stir, kneader, extruder, mixer, heat exchanger, flash tank, delivery pipe etc..Melt polymerization is anti- The example of system and operating condition is answered to be also disclosed in U.S. Patent number 7,365,149,7,547,799,7,619,053 and 7,671, In 165, these patents are discussed above and are incorporated by reference into.

According to method disclosed herein, those skilled in the art can easily be reaction described herein device system and side Method selects acceptable operating condition and specific consersion unit.For example, the standard of reactor apparatus is grasped in melt production facility It can be 50-500 DEG C as temperature.Temperature is higher, and polymerization reaction is faster.It will be understood by those skilled in the art, however, that with temperature It increases, it is possible to create undesirable byproduct of reaction simultaneously mixes in product polycarbonate, and reactive component may degrade.One In a little embodiments, it is sufficient to generate polycarbonate melt polymerization conditions include 100-400 DEG C of temperature (such as 125-350 DEG C, Such as 150 DEG C to 325 DEG C).

In one aspect, the control of reactor assembly is allowed to remove phenol by-product from reaction system.Work as removing When phenol by-product, melting state transesterification reaction can be driven by balanced sequence.It, can direction when removing phenol by-product Establish the molecular weight drive response of polycarbonate.The structure of phenol by-product depends on the diaryl carbonates as carbonate source Ester.

On the other hand, Volatile monohydric phenol can be removed from frit reaction object by distillation, and using polymer as molten Melt residue separation.On the other hand, the useful melting method for being used to prepare polycarbonate, which uses, has electrophilic on aryl The diaryl carbonate of substituent group.The example of particularly advantageous diaryl carbonate with electron-withdrawing substituent includes：Two (4- Nitrobenzophenone) carbonic ester, two (2- chlorphenyl) carbonic esters, two (4- chlorphenyl) carbonic esters, two (methyl salicyl) carbonic esters, two (4- methyl carboxyl phenyl) carbonic ester, two (2- acetylphenyl) carboxylates, two (4- acetylphenyl) carboxylates, or at least wrap A kind of combination containing aforementioned substances.

It in one aspect, can in solid form or in molten form using the reactant of the polymerization reaction of diphenyl carbonate It is added in reactor.Initially reactant is added in reactor and then at reaction conditions by these material mixings to gather Conjunction can carry out in inert gas atmosphere such as nitrogen atmosphere.The charging of one or more reactants can also be after polymerization reaction Phase carries out.Can be by any method known in the art, such as by stirring, complete the mixing of reaction mixture.React item Part includes time, temperature, pressure and the other factors for influencing polymerization ofathe reactants.In general, the aryl carbonate such as dipheryl carbonate of activation Ester can be relative to the total mole number of monomeric unit compound (i.e. aromatic dihydroxy compound and aliphatic diacid or glycol) 0.8-1.3, the molar ratio of more preferable 0.9-1.3 and all subranges therebetween are added.In a specific aspect, diphenyl carbonate Molar ratio with monomeric unit compound is 1.013-1.29, especially 1.015-1.028.

In one aspect, it can be measured by using techniques known in the art such as gel permeation chromatography or other methods The melt viscosity or weight average molecular weight of reaction mixture monitors reaction process.These properties can be surveyed by taking discrete samples Amount, or can be with on-line measurement.After the melt viscosity and/or molecular weight for reaching required, final polycarbonate product can be with It is separated from reactor with solid or melting form.It will be understood by those skilled in the art that being prepared described in preceding sections The method of polycarbonate can be prepared in intermittently or serially method, and method disclosed herein preferably with solvent-free mode into Row, this is the feature of melt polymerization process.The reactor of selection should be ideally self-cleaning, and should minimize and appoint What " hot spot ".It is however possible to use being similar to commercially available vented extruder.

A kind of exemplary polycarbonate compositions are shown below by way of formula (I)：

Polycarbonate is known to the skilled in the art.Polycarbonate, including aromatic carbonate chain units, including have The composition of formula (II) structural unit：

Wherein R¹Group is aromatics, aliphatic series or alicyclic group.Preferably, R¹It is aromatic organic radicals, such as formula (III) Group：

-A¹-Y¹-A²- (III)

Wherein A₁And A₂Respectively monocyclic divalent aryl, Y1 are the abutment with 0,1 or 2 atom, by A1 and A2 points It opens.In an exemplary embodiment, one or more atoms open A1 and A2 points.The illustrative example of this kind of group is- O-、-S-、-S(O)-、-S(O₂- C)-, (O)-, methylene, cyclohexyl-methylene, 2- [2,2,1]-bicycloheptylidene, sub- second Base, isopropylidene, neopentylidene, cyclohexylidene, sub- cyclopentadecane base, sub- cyclo-dodecyl, sub- adamantyl etc..At another In embodiment, no atom opens A1 and A2 points, and illustrative example is bis-phenol.Bridged group Y1 can be alkyl or saturated hydrocarbons Base, such as methylene, cyclohexylidene or isopropylidene.

Polycarbonate can be prepared for example, by melting method and interfacial reaction polymer process, and both methods is all this Known to field.Interfacial process can be used precursor, such as dihydroxy compounds, and only one atom is by A¹And A²It separates.Such as Used herein, term " dihydroxy compounds " includes, such as the bisphenol compound with following logical formula (IV)：

Wherein R^aAnd R^bEach independently represent hydrogen, halogen atom or monovalent hydrocarbon；P and q is each independently the integer of 0-4； And X^aRepresent one of the group of formula (V)：

Wherein R^eAnd R^dIt is independently represented each other hydrogen atom or monovalent linear or cyclic hydrocarbon group, and R^eIt is bivalent hydrocarbon radical.

It can include two (hydroxyaryl) alkane series by the example of formula (IV) bisphenol compound type indicated.It can be by formula (IV) indicate other bisphenol compounds include those wherein X be-O- ,-S- ,-SO- or-SO22-- bisphenol compound.It can use It is indicated in other bisphenol compounds of the polycondensation reaction of polycarbonate by formula (VI).

Wherein, R^fIt is the alkyl that halogen atom or alkyl with 1-10 carbon atom or halogen replace；N is the value of 0-4.When When n is at least 2, R^fIt can be identical or different.Between example by formula (V) bisphenol compound indicated is resorcinol, replaces Diphenol compounds such as 3- methyl resorcinol etc..

Also such as 2,2,2 ', 2 '-tetrahydro -3,3 of bisphenol compound (such as bisphenol-A) that lower formula (VII) indicates can be used, 3 ', 3 '-tetramethyl -1,1 '-two-[IH- indenes] -6 of spiral shell, 6 '-glycol.

The blend of branching polycarbonate and linear polycarbonate and branching polycarbonate can also be used.Branching is poly- Carbonic ester can be prepared by the way that branching agent is added in the course of the polymerization process.These branching agents may include containing at least three kinds of functional groups Polyfunctional group organic compound, the functional group can be hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl, and including at least one The combination of kind foregoing branching agents.Specific example includes trimellitic acid, trimellitic anhydride, trimellitic acid terchoride, three pairs of hydroxyls Diphenylphosphino ethane, isatin-bis-phenol, triphenol TC (1,3,5- tri- ((p-hydroxybenzene) isopropyl) benzene), triphenol PA (4 (4 (1,1- bis- (p-hydroxybenzene)-ethyl) alpha, alpha-dimethylbenzyl) phenol), 4- chloroformyl phthalic anhydride, 1,3,5- benzenetricarboxylic acids and Benzophenone tetrabasic carboxylic acid etc., or the combination including at least one foregoing branching agents.Based on the total weight to polycarbonate in given layer, Branching agent can be added with the level of about 0.05 to about 2.0 weight percent (wt%).

In some aspects of the disclosure, polycarbonate resin has at least about 95% End-cap levels.With the sealing end water Flat polycarbonate resin can usually be prepared by interfacial polymerization method.Purely for example, specifically wherein gather in one kind Carbonic ester is in the interfacial polymerization method of BPA polycarbonate, and BPA polycarbonate is the boundary of the bisphenol-A and phosgene that are catalyzed by amine Face polycondensation reaction preparation.It is less than about 95% other known side with the End-cap levels for the wherein polycarbonate for forming polycarbonate Method (such as melt transesterification method) is compared, and is characterized by having at least about by the polycarbonate that interfacial polymerization method is formed 95% End-cap levels.In some respects, the End-cap levels of polycarbonate resin are at least about 98%, or even at least about 99% End-cap levels.In other respects, polycarbonate resin substantially completely blocks, i.e., sealing end is about 100%.

End-cap levels (EC%) can be determined by the molecular weight concentration of measurement OH group and polycarbonate resin.Example Such as, with reference to the OH group content of total end group of polycarbonate compositions (BPA+PhOH (phenol) from DPC group) (melting PC BPA group) ratio provide EC%.Higher EC% value can be shown that lower OH ends concentration.

In the disclosure, it is shown that the Melt Volume Rate (MVR) of low viscosity grade is about 20cm³/min(1.2Kg-300 DEG C ISO 1133) to about 30cm³The improvement of the impact property of the polycarbonate melt resin of/min.By the way that PC resin will be melted This improvement is realized with other interface PC resin alloys.Compared with traditional end-capping group of melting PC resin, interface PC tree Rouge component has different types of sealing end.Compared with typical case's end group (BPA and phenol) present in the molten resin, interface PC resin End-capping group be based on use phenol and other larger volume molecule such as p -cumylphenols and p-tert-butylphenol.

Increase bulky end groups concentration (by will based on 100% p -cumylphenol block a kind of interface PC grade not It is added in melt PC resin in proportion), with not interfacial polycarbonate compared with substantially similar resin, melt can be improved The impact property of material.

In addition to the foregoing components, the polycarbonate compositions for forming disclosed product may include one kind or more of aequum The additive material that kind is routinely incorporated into such poly carbonate resin composition, condition are selection additives with not significant The required performance of ground adverse effect polycarbonate compositions.Melt polycarbonate resin may include one or more suitable additions Agent, condition be select additive with do not negatively affect significantly melting carbonate composition required performance, such as transparency, Impact strength, thermal stability and/or weatherability.Reaction mixture is optionally for example prepared in moulding article with thermoplasticity application Any conventional additives used are blended.These additives include but is not limited to quencher, UV stabilizer/absorbent, anti-oxidant Agent, heat stabilizer, release agent, colorant, antistatic agent, slip agent, antitack agent, lubricant, prevent turbid dose, colorant, natural oil, Synthetic oil, wax, organic filler, inorganic filler, branching agent and its mixture.The combination of additive can be used.It is being mixed for During the component for forming composition, these additives can be mixed in the suitable time.

In one aspect, the blend that can form melt polycarbonate resin combination and additive helps to add Work blend is to form required moulding article, such as optical goods (CD or lens), auto lamp component etc..Blend can appoint Selection of land contains the required additive of about 0.0001 to about 10 weight %.On the one hand, which contains about 0.0001 to about 1.0 weight Measure the required additive of %.

The composition can further comprise antisatic additive.Illustrative antisatic additive may include polysubstituted The halogenated carbon sulfonate of compound.In one aspect, the composition may include the perfluoro butyl sulfonic acid tetrabutyl

Illustrative ultraviolet (UV) absorbent or UV protective agent may include, but be not limited to, salicylic acid UV absorbent, hexichol first Ketone UV absorbent, benzotriazole UV absorbers, cyanoacrylate UV absorber and its mixture.Illustrative UV protective agent/ Absorbent may include 2- (2- hydroxyl -5- t-octyl phenyl) benzotriazole or phenol, 2,-two (6- (2H-2- benzo of 2 '-methylene Triazol radical) -4- (1,1,3,3- tetramethyl butyl)).The example of heat-resisting stabilizing agent includes but is not limited to phenol stabilizers, organic sulfur Ether stabilizer, organic phosphite stabilizers, hindered amine stabilizer, epoxy stabilizer and its mixture.Heat-resisting stabilizing agent can be with It is added in the form of solid or liquid.The example of release agent includes but is not limited to natural and synthesis alkane, polyethylene wax, carbon fluorine Compound and other hydro carbons release agents；Stearic acid, hydroxy stearic acid and other higher fatty acids, hydroxy fatty acid and other fat Sour release agent；Stearic amide, ethylene (stearmide) and other fatty acid amides, alkylidene difatty acid amide and its His fatty acid amide release agent；Stearyl alcohol, hexadecanol and other fatty alcohols, polyalcohol, polyethylene glycol, polyglycereol and other alcohols Release agent；Butyl stearate, the low-carbon-ester of pentaerythritol tetrastearate and other fatty acid, fatty acid polyol ester, The macrogol ester of fatty acid and other aliphatic ester release agents；Silicone oil and other siloxane release agents and any of above Mixture.Colorant can be pigments or dyes.Inorganic colourant and toner can be used alone or be applied in combination.Branch The example of agent includes but is not limited to THPE (4,4 ', 4 "-ethylidine trisphenol (phenol, 4,4 ', 4 "- Ethylidynetris)), 9- carboxyl octadecane diacid or 1,3,5- benzenetriols.Additive such as plasticizer, lubricant and/or de- Mould agent addition agent is usually used with the amount of about 0.01 weight percent (wt%) of polycarbonate blend composition to about 20wt%, Optional about 0.5wt% to about 10wt%.In one aspect, release agent is glycerol tristearate.

Further, disclosed blending thermoplastic compounds can further include main anti-oxidant or " stablize Agent " (such as hindered phenol) and optional secondary antioxidant (such as phosphate and/or thioesters).In one aspect, antioxidant is Main anti-oxidant, secondary antioxidant or combinations thereof.In even further aspect, main anti-oxidant is selected from hindered phenol and Zhong Fangji Amine, or combinations thereof.Exemplary antioxidants may include 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl conduct Sterically hindered phenolic antioxidant.Antioxidant usually can be to be blended the about 0.01wt% to about 3wt% of thermoplastic compounds Amount use, optionally about 0.05wt% to about 2.0wt%.In some respects, hydrolysis and heat stabilizer can be with melt polycarbonates Resin is used together.Heat stabilizer is usually used with the amount of the about 0.01wt% of polycarbonate blend composition to about 5wt%, is appointed Select about 0.05wt% to about 2.0wt%.

Further, anti-dripping agent also may be present.Further, anti-dripping agent is styrene-propene The polytetrafluoroethylene (PTFE) of lonitrile copolymer encapsulating.Illustrative anti-dripping agent may include forming fibrinogen or forming the fluorine-containing of non-protofibre Polymer, such as polytetrafluoroethylene (PTFE) (PTFE) or the PTFE being encapsulated in SAN for TSAN.Anti-dripping agent can be with about The amount of 0.01wt%55 about 3wt% exists.

The product of manufacture

Melt polycarbonate resin with interfacial polycarbonate component as disclosed herein can be used as according only to interface The substitute of the polycarbonate resin of polymerization preparation.In even further aspect, poly- carbonic acid is melted as disclosed herein The property of ester resin may be particularly useful for being subjected to long-time weathering, abrasion or the application used by the product that it is formed.Therefore, have There is the melt polycarbonate resin of interface polycarbonate component can be used to form usually to be formed by interfacial polymerization polycarbonate resin Polycarbonate resin product.Transparency, mobility and the impact property of product can be with the matter that are obtained according to interfacial polymerization method Amount is suitable.

Therefore, the disclosed melt polycarbonate resin with interfacial polycarbonate component can be used for manufacturing for electricity Son, automobile, imaging, health care or Optical devices product.Equipment and application may include：Antifog window；For illuminating the lens of application And/or transparency cover, such as automotive lighting, street lighting, outdoor lighting and efficient illumination, such as Light-emitting diode LED application, have Machine LED application, for LED/LCD display black lamp door frame, the black lamp holder for LED/LCD display, LCD it is aobvious Show that device, fluorescent illumination application, gas discharge illumination application and neon lamp application can produce less compared with conventional light source Heat as byproduct；Optical lens comprising camera and observation camera lens, such as mobile telephone camera, and be used for Digital still photographic camera, mirror, telephoto lens, binoculars, vehicle camera camera lens and article of eyewear, such as glasses, Including sunglasses, sunglasses eyeglass, goggles, Sports spectacles, mask and prescription lens.Electro-optical device may also include cathode-ray Pipe, fluorescent lamp, gas discharge light source and neon lamp and light emitting diode, Organic Light Emitting Diode, plasma and liquid crystal display.

Following application may be particularly useful in by the product that the composition and method of the disclosure are formed：Mobile phone, mobile meter Calculate equipment, camera, video recorder, projector, correcting lens, diffusing globe or duplicator.In further example, poly- carbonic acid Ester resin can be used to form the product in the device for the lens of such as portable electronic application, including mobile phone, camera, a Personal digital assistant, DVD player and recording device etc..In addition, the product made of disclosed composition and product also can be used In various applications, including thin wall product, wherein transparency, accuracy, the machine including impact strength defined by degree of reproducibility The holding of tool performance and accurate optical property are required.In further example, the optically transparent poly- carbonic acid of melting Ester articles can weather-proof or high temperature resistant and full sun conditions outdoor weather exposure condition.Product can be used for protecting is located outside work for a long time Make the photoelectric device in environment, such as solar battery, and keeps impact strength.

In one aspect, this disclosure relates to shape, form or moulding article, it includes according to melt polymerization disclosed herein The polycarbonate compositions of method preparation.Polycarbonate compositions can be molded as useful molded article, example by various methods If injection molding, extrusion molding, rotational molding, blow molding and thermoforming are to form product.Polycarbonate compositions as described herein It may be made as the component of film and sheet material and laminated system.Product comprising disclosed polycarbonate compositions can be but It is not limited to computer and business machine shell, such as the shell for high-end laptop PC, monitor, hand-held electronics Device housings, for example, the shell for smart phone, tablet computer, LCD display, CD and video disc, musical instruments it is electrical, The component of connector and lighting device, ornament, household electrical appliance etc..

In further aspect, moulding article can be used for manufacturing the device in medical health field.In yet a further aspect, The non-limiting example that the such device of disclosed mixing thermoplastic composition can be used in medical health field includes Drug delivery system, syringe, cock, syringe adapter, kidney or blood care device, blood filter, dialysis shell, thoroughly The shell of analyzer table, pump, novopen or mask for shell of dialysing.

In further aspect, moulding article can be used for manufacturing the device in automotive field.In further aspect, automobile neck It can the use of the non-limiting example of this device of disclosed mixing thermoplastic compounds include inside the vehicle certainly in domain Cruise control, headlight sensor, automobile decoration circle, automobile reflecting mirror, windscreen wiper sensor and door/window is adapted to open It closes.It can be used for outside vehicle in further aspect, disclosed mixing thermoplastic compounds.The various elements of present disclosure Combination is comprising in this disclosure, such as the element combination of the dependent claims dependent on identical independent claims.

Manufacturing method

In various aspects of the disclosure, melt polymerization can carry out in typical polymerization unit, for example, one or Multiple continuous-stirring reactors (CSTR), plug flow reactor, line wetting landing polymer reactor, freely falling body polymerization reaction Device, wiping film polymer reactor,Mixer, single screw rod or double screw extruder or combination above-mentioned.? On one side, the Volatile monohydric phenol generated in situ can be removed from frit reaction object by distillation, and using polymer as Molten residue separation.

The melt polycarbonate resin combination of the disclosure can be blended by a variety of methods with mentioned component, including with boundary Face polycarbonate component is blended, and the method includes uniformly mixing material with any other additive needed for preparation.By The availability of melt blending equipment in commercial polymer process equipment, it is usually preferred to method for melt processing.Add in this melting In work method, the illustrative example of the equipment used includes：Rotating Vortex and reverse rotation extruder, are total to single screw extrusion machine The extrusion equipment of kneader, disc type packing machine and various other types.It is preferred that the temperature of melt in the method for the present invention is minimized, To avoid resin excessive degradation.It is generally desirable to keep in molten resin composition melting temperature about 230 DEG C to about 350 DEG C it Between, although higher temperature can be used, condition is to keep very short the residence time of resin in process equipment.In some implementations In scheme, the composition of melt-processed leaves process equipment, such as extruder by the small outlet opening in die head.By making strand Resulting molten resin strand is cooled down by water-bath.Cooling strand can be cut into little particle for pack and further locate Reason.

Composition can manufacture by various methods, including the skill in batches or continuously using kneader, extruder, mixing machine etc. Art.For example, double screw extruder, which can be used, in composition forms melt blended material.In some embodiments, at least some groups Divide is that sequence is added.Or the sequence addition of component can be completed by repeated processing.Component selected by pre-extruded can be passed through Prepare composition.Then it can be squeezed out using second and mix the component of pre-extruded with remaining component.

As described herein, this disclosure relates to the method for preparing polycarbonate compositions by melt polycarbonate polymerization. Any of method can be used, combine various ingredients to form fluoropolymer resin, to form the composition of the disclosure.One A aspect first mixes component in super mixer.Other low sheraing processes (including but not limited to hand mix) can also To realize this mixing.Then mixture is sent into the throat of double screw extruder by hopper.Or one or more components It can be mixed in composition by throat and/or be fed directly into extruder in downstream by side sizer.Extruder behaviour The temperature of work is usually above the temperature for keeping composition flowing required.Extrudate is cooled down in the sink and is granulated immediately.Work as cutting The pellet so prepared when extrudate can according to need for quarter inch it is long or shorter.This pellet can be used for subsequent Molding, forming or molding.In one aspect, blend composition is formed by squeezing out to be blended.

Furthermore, it is to be understood that unless expressly stated otherwise, being otherwise never intended to be construed to want by any method as described herein It asks and its step is executed with particular order.Therefore, it is practically without in claim to a method and states the sequence that is followed of its step In the case of, or when being not particularly illustrated the step in claim or specification and will be restricted to specific sequence, then absolutely It is not intended to infer a sequence in any way.This is suitable for any possible basis for interpretation non-clearly, including：About step Logical problem in terms of arrangement or operating process；The simple meaning obtained from grammatical organization or punctuation mark；And specification Described in aspect quantity or type.

Definition

It should be understood that terms used herein are only used for the purpose of description particular aspects, rather than it is restrictive.Such as specification Used in claims, term "comprising" may include the aspect of " consist of " and "consisting essentially of ...".Unless In addition it defines, otherwise all technical and scientific terms used herein has logical with disclosure those of ordinary skill in the art The identical meaning understood.In the present specification and claims, many terms defined herein will be referred to.Herein All publications referred to are both incorporated herein by reference, with disclosure and description method relevant to cited publication and/ Or material.

As used in specification and appended, singular " one (a) " " one (an) " and " should It (the) " include plural referents, unless the context is clearly stated.Thus, for example, referring to that " polycarbonate " includes two kinds Or more as polycarbonate mixture.In addition, for example, referring to that filler includes two or more such fillers Mixture.

Range can be expressed as herein from " about " particular value, and/or to " about " another particular value.Work as expression It on the other hand include from a particular value and/or to another particular value when such range.Similarly, when by using elder generation When value is expressed as approximation by row word " about ", it will be understood that on the other hand the particular value is formed.It will be further understood that, each range Endpoint is all important relative to another endpoint, and independently of another endpoint.It should also be understood that disclosed herein is many Value, and other than value itself, each value is also disclosed as " about " particular value herein.For example, if disclosing value " 10 " then also disclose " about 10 ".It should also be understood that also disclosing each unit between two discrete cells.For example, if public 10 and 15 have been opened, then have also disclosed 11,12,13 and 14.

" optional " or " optionally " refer to the event then described, condition, component or feelings as it is used herein, term Condition may occur or may not occur, and the description includes the event or the example happened and its reality not occurred Example.

As used herein, term or phrase " effective ", " effective quantity " or " right ... effective condition ", which refers to, is able to carry out table Up to a effective amount of function or the amount or condition of property.As described below, required exact amount or specified conditions will be according to being identified Variable (such as material therefor and observed processing conditions) and different aspect change.Therefore, it is not always able to specified essence True " effective quantity " or " effective condition ".It should be appreciated, however, that those of ordinary skill in the art can using only routine experiment To be readily determined suitable effective quantity.

It discloses used in the component material for being used to prepare the open composition of the disclosure and method disclosed herein Composition itself.Disclosed herein is these and other materials, and it is to be understood that when the combination, the subset, phase that disclose these materials Whens interaction, group etc., although every kind of different individual and collective's combination and permutation cannot clearly disclosing these compounds With specific reference to, but each of herein special consideration should be given to and description.For example, if it is open and discuss specific compound and The many modifications carried out to many molecules for including the compound are discussed, then it is particularly contemplated that every kind of compound is combined With arrangement and possible modification, unless otherwise indicated.Therefore, if disclosing molecule A, B and C and a kind of point The example of sub- D, E and F and combination molecule, then disclose A-D, even when not enumerating individually each, each is independent Consider with common, it is meant that combination A-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F are considered disclosed.Equally, also public These any subset or combination are opened.Thus, for example, the subgroup that will consider open A-E, B-F and C-E.The concept is suitable for All aspects of the application include but is not limited to the step made and used in the method for the composition of the disclosure.Therefore, if In the presence of the various additional steps that can be executed, then it should be understood that each of these additional steps can use the side of the disclosure The combinations of any particular aspects or aspect of method executes.

Parts by weight in specification and appended about element-specific or component in composition or product mention And indicate any other element in the element or component and composition or product or the weight indicated by weight between component Magnitude relation.Therefore, in the composition containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are with 2: 5 weight ratio In the presence of, and regardless of whether comprising other components, all with the presence of such ratio.

Unless otherwise stated, the weight percent of component is based on the preparation or composition for wherein including the component Total weight.For example, if element-specific or component in composition or product have 8 weight %, it should be understood that the percentage with Total composition percentage is 100% related.

Compound disclosed herein is described using standardized denomination.For example, any position not being substituted by any indicated group It sets and is interpreted as its valence state key as shown in or hydrogen atom filling.Dash ("-") not between letter or symbol is used In the tie point for indicating substituent group.For example,-CHO is connected by the carbon of carbonyl.Unless otherwise defined, otherwise skill used herein Art and scientific term have meaning identical with the normally understood meaning of disclosure those skilled in the art.

Term " comparable " as used herein can refer to the similitude between given resin combination as described herein.Quite The quantized value that can be used for representation property or Given Properties it is similar to another property or match.

As used herein, term " substantially the same reference portfolios object " refers to the group essentially identical with the present composition Object is closed, is grouped as by essentially identical ratio and group but there is no single components.

Term " transparency " as used herein can refer to the level of transmittance of resin combination, greater than 50%, including Exemplary transmission rate value at least 60%, 70%, 80%, 85%, 90% and 95%, or any range of going out is worth by above-mentioned example Transmittance values.In some instances, resin combination can show the transmittance values greater than 85%.It can be according to the side ASTM The transmissivity of the disclosed resin combination of method D1003 measurement.

As used herein, term " number-average molecular weight " or " Mn " are used interchangeably, and refer to all polymer in sample The statistical average molecular weight of chain, and be defined by the formula：

Wherein M_iIt is the molecular weight of chain, N_iIt is the chain quantity of the molecular weight.It can be by well known within the skill of those ordinarily skilled Method measure the polymer such as Mn of carbonate polymer or polycarbonate-PMMA copolymer.It should be understood that such as this paper institute With Mn is to be measured by gel permeation chromatography and calibrated with polycarbonate standard.For example, gel permeation chromatography can be with Using the styrene-divinylbenzene column of crosslinking, carried out under the sample concentration of 1 mg/ml with suitable mobile phase solvent.

As used herein, term " weight average molecular weight " or " Mw " are used interchangeably, and are defined by the formula：

Wherein M_iIt is the molecular weight of chain, N_iIt is the chain quantity of the molecular weight.Compared with Mn, Mw is being determined to molar mass average The molecular weight of given chain is considered when the contribution of value.Therefore, the molecular weight of given chain is bigger, and chain is bigger to the contribution of Mw.Ying Li Solution, as used herein, Mw is measured by gel permeation chromatography.In some cases, it is measured by gel permeation chromatography Mw is simultaneously calibrated with polycarbonate standard.In other respects, Mw is measured by gel permeation chromatography and uses polystyrene standard Object calibration.The styrene-divinylbenzene column of crosslinking can be used in gel permeation chromatography, dense in the sample of about 1 mg/ml Degree is lower to be carried out with mobile phase solvent appropriate.

Aspect：

In all fields, this disclosure relates to and including at least following aspect.

The product that aspect 1. is formed by composition, the composition include：The poly- carbonic acid of melting from diphenyl carbonate Ester resin；With the interfacial polycarbonate resin mixed with melt polycarbonate resin, wherein the composition is at 1.2kg and 300 DEG C Under melt volume rate be about 20cm³/ 10min to about 30cm³/ 10min, wherein in the composition and substantially by melting poly- carbon It is shown within the scope of the Ductile-brittle transition temperature of the comparative composition of acid ester resin composition by the product that the composition is formed IZOD notched impact properties is greater than the IZOD notched impact properties of the product formed by the comparative composition.

The product that aspect 2. is formed by composition, the composition include：The poly- carbonic acid of melting from diphenyl carbonate Ester resin；With the interfacial polycarbonate resin mixed with melt polycarbonate resin, wherein the composition is at 1.2kg and 300 DEG C Under melt volume rate be about 20cm³/ 10min to about 30cm³/ 10min, wherein the temperature in about -20 DEG C to about 0 DEG C of range IZOD notched impact properties is shown by the product that the composition is formed under degree to be greater than substantially by melt polycarbonate resin group At comparative composition formed product IZOD notched impact properties.

Product described in any one of 3. aspect 1-2 of aspect, wherein the product is transparent.

Product described in any one of 4. aspect 1-3 of aspect, wherein interfacial polycarbonate resin have phenol sealing end or Any larger volume group such as p -cumylphenol, p-tert-butylphenol or combinations thereof.

Product described in any one of 5. aspect 1-4 of aspect, wherein melt of the composition at 1.2kg and 300 DEG C Volume fraction is about 21cm³/ 10min to about 26cm³/10min。

Product described in any one of 6. aspect 1-4 of aspect, wherein melt of the composition at 1.2kg and 300 DEG C Volume fraction is 26cm³/10min。

Product described in any one of 7. aspect 1-6 of aspect, wherein being shown at about -5 DEG C by the product that composition is formed IZOD notched impact properties is greater than the IZOD of the product substantially formed by the comparative composition that melt polycarbonate resin forms Notched impact properties.

Product described in any one of 8. aspect 1-6 of aspect, wherein by institute at a temperature of between about -15 DEG C to about 0 DEG C The product for stating composition formation shows IZOD notched impact properties and is greater than the ratio being substantially made of melt polycarbonate resin Compared with the IZOD notched impact properties for the product that composition is formed.

Product described in any one of 9. aspect 1-6 of aspect, wherein by institute at a temperature of between about -10 DEG C to about -5 DEG C The product for stating composition formation shows IZOD notched impact properties and is greater than the ratio being substantially made of melt polycarbonate resin Compared with the IZOD notched impact properties for the product that composition is formed.

Product described in any one of 10. aspect 1-9 of aspect, wherein the poly- carbon of whole relative to 100wt% in composition Acid ester resin, the composition include the melt polycarbonate resin of about 20wt% to about 80%.

Product described in any one of 11. aspect 1-9 of aspect, wherein the poly- carbon of whole relative to 100wt% in composition Acid ester resin, the composition include about 20wt% melt polycarbonate resin and about 80% interfacial polycarbonate resin.

Product described in any one of 12. aspect 1-9 of aspect, wherein the poly- carbon of whole relative to 100wt% in composition Acid ester resin, the composition include about 40wt% melt polycarbonate resin and about 60% interfacial polycarbonate resin.

Product described in any one of 13. aspect 1-9 of aspect, wherein the poly- carbon of whole relative to 100wt% in composition Acid ester resin, the composition include about 60wt% melt polycarbonate resin and about 40% interfacial polycarbonate resin.

Product described in any one of 14. aspect 1-9 of aspect, wherein the poly- carbon of whole relative to 100wt% in composition Acid ester resin, the composition include about 80wt% melt polycarbonate resin and about 20% interfacial polycarbonate resin.

Product described in any one of 15. aspect 1-14 of aspect, wherein the product is in automobile application.

Product described in the aspect of aspect 16. 15, wherein the product includes automobile decoration circle, auto mirror, in automobile Decorations or automobile exterior.

Product described in any one of 17. aspect 1-14 of aspect, wherein the product is in electrical and illumination application.

Product described in the aspect of aspect 18. 17, wherein the product include electronic component, the electrical enclosure including MCCD, For the black lamp door frame of LED/LCD display, for black lamp holder, lighting device or the illumination of LED/LCD display Cover.

Product described in any one of 19. aspect 1-14 of aspect, wherein the product is in health care application.

Product described in 20. aspect 19 of aspect, wherein the product includes drug delivery system.

Product described in 21. aspect 20 of aspect, wherein the product includes syringe, cock or syringe adapter.

Product described in 22. aspect 19 of aspect, wherein the product includes kidney or blood care device.

Product described in 23. aspect 22 of aspect, wherein the product includes blood filter, dialysis shell, for dialysing The instrument of shell, pump or novopen for shell of dialysing.

Product described in 24. aspect 19 of aspect, wherein the product includes mask.

Product described in any one of 25. aspect 1-14 of aspect, wherein the product is in appliance applications.

Product described in 26. aspect 25 of aspect, wherein the product includes the electronic component for consumption electronic product Shell.

Product described in the aspect of aspect 27. 26, wherein the product include for personal computer, laptop computer, Personal tablet computer, mobile phone, LCD display, CD or video disc electronic building brick shell.

Product described in any one of 28. aspect 1-14 of aspect, wherein the product is in eyewear applications.

Product described in 29. aspect 28 of aspect, wherein the product includes sunglasses eyeglass, Sports spectacles or safe eye Mirror.

The method of any one of 1-14 product in terms of a kind of formation of aspect 30..

A kind of composition of aspect 31., it includes：From the melt polycarbonate resin of diphenyl carbonate；With with melting Polycarbonate resin mixing interfacial polycarbonate resin, wherein melt volume rate of the composition at 1.2kg and 300 DEG C be About 20cm³/ 10min to about 30cm³/ 10min, wherein the comparison in composition and being substantially made of melt polycarbonate resin IZOD notched impact properties is shown by the product that the composition is formed within the scope of the Ductile-brittle transition temperature of composition to be greater than By the IZOD notched impact properties for the product that the comparative composition is formed,.

A kind of composition of aspect 32., it includes：From the melt polycarbonate resin of diphenyl carbonate；With with melting Polycarbonate resin mixing interfacial polycarbonate resin, wherein melt volume rate of the composition at 1.2kg and 300 DEG C be About 20cm³/ 10min to about 30cm³/ 10min, wherein in about -20 DEG C to about 0 DEG C of range at a temperature of by the composition shape At product show IZOD notched impact properties and be greater than the comparative composition shape that is substantially made of melt polycarbonate resin At product IZOD notched impact properties.

Composition described in any one of 33. aspect 31-32 of aspect, wherein being transparent by the product that the composition is formed 's.

Composition described in any one of 34. aspect 31-33 of aspect, wherein interfacial polycarbonate resin has to cumyl benzene The sealing end of phenol, p-tert-butylphenol, phenol, phosgene or combinations thereof.

Composition described in any one of 35. aspect 31-34 of aspect, wherein the composition is in 1.2kg and 300 DEG C of following table Reveal about 21cm³/ 10min to about 26cm³The melt volume rate of/10min.

Composition described in any one of 36. aspect 31-34 of aspect, wherein the composition is at 1.2kg and 300 DEG C Melt volume rate is 26cm³/10min。

Composition described in any one of 37. aspect 31-36 of aspect, wherein the system formed at about -5 DEG C by the composition Product show IZOD notched impact properties and are greater than the system substantially formed by the comparative composition that melt polycarbonate resin forms The IZOD notched impact properties of product.

Composition described in any one of 38. aspect 31-36 of aspect, wherein at a temperature of between about -15 DEG C to about 0 DEG C It shows IZOD notched impact properties by the product that the composition is formed and is greater than substantially to be made of melt polycarbonate resin Comparative composition formed product IZOD notched impact properties.

Composition described in any one of 39. aspect 31-36 of aspect, wherein the temperature between about -10 DEG C to about -5 DEG C Under by the product that the composition is formed show IZOD notched impact properties be greater than substantially by melt polycarbonate resin group At comparative composition formed product IZOD notched impact properties.

Composition described in any one of 40. aspect 31-39 of aspect, wherein the whole relative to 100wt% in composition Polycarbonate resin, the composition include the melt polycarbonate resin of about 20wt% to about 80%.

Composition described in any one of 41. aspect 31-39 of aspect, wherein the whole relative to 100wt% in composition Polycarbonate resin, the composition include about 20wt% melt polycarbonate resin and about 80% interfacial polycarbonate tree Rouge.

Composition described in any one of 42. aspect 31-39 of aspect, wherein the whole relative to 100wt% in composition Polycarbonate resin, the composition include about 40wt% melt polycarbonate resin and about 60% interfacial polycarbonate tree Rouge.

Composition described in any one of 43. aspect 31-39 of aspect, wherein the whole relative to 100wt% in composition Polycarbonate resin, the composition include about 60wt% melt polycarbonate resin and about 40% interfacial polycarbonate tree Rouge.

Composition described in any one of 44. aspect 31-39 of aspect, wherein the whole relative to 100wt% in composition Polycarbonate resin, the composition include about 80wt% melt polycarbonate resin and about 20% interfacial polycarbonate tree Rouge.

The method of composition described in any one of 31-44 in terms of a kind of formation of aspect 45..

Without being further described, it is believed that description herein can be used to utilize the disclosure in those skilled in the art. Including following embodiment to provide increased guidance to the technical staff for practicing disclosed field claimed.It is provided Embodiment only represents this work and facilitates the guidance of the disclosure.Therefore, these embodiments are not intended in any way Limit the disclosure.

In entire the application, various publications are referred to.The complete disclosure of these publications is incorporated by reference into Into the application, so that the status of its fields is described more fully with.In order to what is discussed in sentence based on bibliography Material wherein included, disclosed bibliography is also individually and in particular by being incorporated herein by reference.Herein is any Content is not necessarily to be construed as recognizing that the disclosure haves no right to take the lead in by formerly disclosed such publication.In addition, provided herein Publication date may be different from the practical publication date, this may need independent confirmation.

Embodiment

Just how to carry out and evaluate methods, devices and systems disclosed and claimed herein, propose following embodiment with Complete disclosure and description is provided to those of ordinary skill in the art, and is intended to purely be exemplary and be not intended to be limited to this It is open.The accuracy about digital (for example, amount, temperature etc.) is endeavoured to ensure, it is contemplated that some errors and deviation.It removes Non- to be otherwise noted, otherwise number is parts by weight, and temperature is degree Celsius (DEG C) or environment temperature, and pressure is or close to atmosphere Pressure.

Generating the melt of different proportion and interface resin by offline blending step in an extruder has an identical viscosities (MVR=26cm³/ 10min-1.2Kg) sample sets.Term " offline " is defined as the discontinuous step in Blending Processes, with Online blending additive is opposite in an extruder in continuous process.Sample is generated by adjusting polymer ratio, as shown in table 1：

The PC sample and PC type generated in 1. extruder of table

The Melt Volume Rate (MVR) of PC1 (melt) and PC2 (interface), fries content and sealing end are than as shown in table 2.

Table 2. is 26cm in MVR³Property (the lower specification limit 23.5cm of PC1 (melt) and PC2 (interface) when/10min³/ 10min, upper specification limit 28.5cm³/10min)

For the sample in the table 1 that is generated in EMT extruder and the step according to described in iso standard：In 3mm and Impact behavior (IZOD notch shock ISO 180-1A) is evaluated under 7 different temperatures.It is 26cm for MVR³/ 10min (1.2Kg, 300 DEG C of ISO 1133), test sample as the result is shown in Fig. 1.

Fig. 2 and Fig. 3 illustrates the effect for introducing interfacial polycarbonate with difference.Fig. 2 is provided as temperature funtion Impact property for different amounts of PC1 melt PC resin diagram.Fig. 3 provides the impact observed at different temperatures Can diagram, the impact property as large volume present in sample end-capping group (bisphenol-A, BPA and p -cumylphenol, PCP the function of amount).Table 3 shows the impact property of the sample with different amounts of melt polycarbonate.

Average impact performance of 3. sample blends of table at not same amount melt PC1.

Higher impact property is observed when as shown in Fig. 2, usually there are a greater amount of interface PC2 in the sample.Such as Fig. 3 It is shown, the impact strength observed relative in sample with or without large volume in blend existing for the PC2 resin of interface The plotted as percentage of end group.The figure, which allows to determine, to be obtained and blend median surface needed for the comparable impact property of interface PC resin The minimum of PC2 resin.In some aspects, comprising at least 40% interface PC2 resin, (47.8% substantially in composition formula is blended Product end group), to realize the identical ductility of melt material at 0 DEG C, 5 DEG C and 10 DEG C.For lower temperature, such as -5 DEG C With -10 DEG C, impact property level increases with the addition of interface PC2, until the content of interface resin is about 60%.

Fig. 4-7 further illustrate 10 DEG C, 5 DEG C, 0 DEG C and-5 DEG C at a temperature of be added into melt polycarbonate resin Influence of the interfacial polycarbonate resin to impact property.Fig. 4 and Fig. 5 respectively illustrates impact of the sample at 10 DEG C and 5 DEG C Energy.Curve be from the data point of impact property it is extrapolated come.As shown, about 70% interfacial polycarbonate can be will be up to It is added in melt polycarbonate without the impact property for influencing molten resin, impact property is made to be maintained at ideal 40kJ/m² More than.Fig. 6 and 7 respectively illustrates impact property of the sample at 0 DEG C and -1 DEG C.Here, it for example, at 0 DEG C, can will be up to The interfacial polycarbonate of 45wt% is added in molten resin, while required impact strength being kept to be greater than about 40kJ/m²。

It is surprising that the impact property observed is also shown more than the impact property calculated.For calculating impact The mathematical formulae of energy is as follows：

Impact strength=(wt.%_{Pc melting}* impact strength_{PC melting})+(wt.%_{The interface PC}* impact strength_{The interface PC})

It is 45kJ/ in the impact force that the interface 50wt.% PC and 50wt.% melting PC is observed at 5 DEG C as example m².According to the formula, the impact value that the linear weight combination based on resin value calculates will be 32kJ/m²[or (0.5*52)+(0.5* 12)].Therefore, with 32kJ/m²Calculated value compare, 45kJ/m²Observation indicate impact property increase about 40%.

According to these as a result, it may be concluded that compared with the impact behavior of Standard melt polycarbonate, according to melt There is positive influence to the impact property of final resin with the blending strategy of interface resin.Use the strategy by two kinds of mixing The resin of type is (for example, the 20-30cm under 1.2kg (300 DEG C)³/ 10min) it is produced at low temperature with better low viscosity etc. The material of the impact property of grade.

It will be apparent to one skilled in the art that without departing from the scope or spirit of the present disclosure, it can To carry out various modifications and change in the disclosure.In view of specification disclosed herein and practice, other aspects of the disclosure It will be apparent to those skilled in the art.Specification and example are intended to be considered only as illustratively, the disclosure True scope and spirit indicated by appended claims.

The range that the disclosure can patent is defined by the claims, and may include that those skilled in the art expect Other examples.If these other examples have the structural element not different from the literal language of claim, Huo Zheru They include equivalent structural elements with the literal language of claim without essential difference to fruit, then these other examples intention is being weighed In the range of benefit requires.

Claims

1. the product formed by composition, the composition include：

From the melt polycarbonate resin of diphenyl carbonate；With

The interfacial polycarbonate resin mixed with the melt polycarbonate resin,

Wherein melt volume rate of the composition at 1.2kg and 300 DEG C is about 20cm³/ 10min to about 30cm³/ 10min, And

The ductile brittle for the comparative composition being wherein made of in the composition and substantially the melt polycarbonate resin IZOD notched impact properties is shown greater than the comparative composition by the product that the composition is formed in transformetion range The IZOD notched impact properties of the product of formation.

2. the product formed by composition, the composition include：

From the melt polycarbonate resin of diphenyl carbonate；With

The interfacial polycarbonate resin mixed with the melt polycarbonate resin,

Wherein in about -20 DEG C to about 10 DEG C of range at a temperature of IZOD notch shown by the product that the composition is formed Impact property is greater than the IZOD notch of the product substantially formed by the comparative composition that the melt polycarbonate resin forms Impact property.

3. product of any of claims 1-2, wherein the product is transparent.

4. product of any of claims 1-3, wherein the interfacial polycarbonate resin has to cumylphenol, to uncle The sealing end of butylphenol, phenol or combinations thereof.

5. product of any of claims 1-4, wherein melt volume of the composition at 1.2kg and 300 DEG C Rate is about 21cm³/ 10min to about 26cm³/10min。

6. product of any of claims 1-5, wherein about 10 DEG C to about -10 DEG C at a temperature of by the composition The product of formation shows IZOD notched impact properties and is greater than the comparative group being substantially made of the melt polycarbonate resin Close the IZOD notched impact properties for the product that object is formed.

7. product of any of claims 1-6, wherein the poly- carbonic acid of whole relative to 100wt% in the composition Ester resin, the composition include the melt polycarbonate resin of about 20wt% to about 80%.

8. product of any of claims 1-6, wherein the poly- carbonic acid of whole relative to 100wt% in the composition Ester resin, the composition include about 20wt% the melt polycarbonate resin and about 80% the interfacial polycarbonate Resin.

9. product of any of claims 1-6, wherein the poly- carbonic acid of whole relative to 100wt% in the composition Ester resin, the composition include about 40wt% the melt polycarbonate resin and about 60% the interfacial polycarbonate Resin.

10. product of any of claims 1-6, wherein the poly- carbon of whole relative to 100wt% in the composition Acid ester resin, the composition include about 60wt% the melt polycarbonate resin and about 40% the poly- carbonic acid in the interface Ester resin.

11. product of any of claims 1-6, wherein the poly- carbon of whole relative to 100wt% in the composition Acid ester resin, the composition include about 80wt% the melt polycarbonate resin and about 20% the poly- carbonic acid in the interface Ester resin.

12. product of any of claims 1-11, wherein the product is in automobile application.

13. product described in claim 12, wherein the product constitutes at least part of automotive interior or outside, including vapour Vehicle case ring, auto mirror, automobile interior decoration or automobile external.

14. product of any of claims 1-11, wherein the product is in electrical and illumination application.

15. product described in claim 14, wherein the product includes electronic component, electronic accessories, shows for LED/LCD Black lamp door frame, black lamp holder, lighting device or the illuminating cover for LED/LCD display of device.

16. product of any of claims 1-11, wherein the product is in health care application.

17. product described in claim 16, wherein the product includes syringe, cock, syringe adapter, blood filtration Device, dialysis shell, the instrument for shell of dialysing, the pump, novopen or mask for shell of dialysing.

18. product of any of claims 1-11, wherein the product is in glasses and appliance applications.

19. product described in claim 18, wherein the product include sunglasses eyeglass, Sports spectacles or safety glasses or Electricity for personal computer, laptop computer, personal tablet computer, mobile phone, LCD display, CD or video disc The shell of subcomponent.

20. a kind of method for forming product described in any one of claim 1-19.